Hair dye blend of a yellow component and red components and/or blue components

ABSTRACT

A HAIR DYEING COMPOSITION CONTAINING A YELLOW DYE COMPONENT AND/OR A BLUE COMPONENT AND/OR A RED COMPONENT IN WHICH THE YELLOW COMPONENT IS CHANGED, DESTROYED, LEACHED OR OTHERWISE REMOVED FROM HAIR TO WHICH SAID DYEING COMPOSITION HAS BEEN APPLIED AT THE SAME RATE AS SAID RED AND/OR BLUE COMPONENTS.

United States Patent ABSTRACT OF THE DISCLOSURE A hair dyeing composition containing a yellow dye component and/ or a blue component and/ or a red component in which the yellow component is changed, de-

3,733,175 Patented May 15., 1973 The class of dyes that are suitable for the purposes of the present invention are a class of yellow dyes .that are characterized by the fact that they are less tenaciously held in the hair after long periods of wear or are less resistant to change or destruction than the yellow hair dye components which have been conventionally used in hair dye compositions.

16 Claims stroyed, leached or otherwise removed from hair to which said dyeing composition has 'been applied at the same rate as said red and/ or blue components. a

This application is a continuation of application Ser. No. 517,987 filed J an. 3, 1966, now abandoned.

This invention relates to hair dye compositions and to processes for dyeing hair with the same. More particularly, it relates to processes and compositions of this character which are particularly suitable for direct dyeing of hair, i.e. dyeing which does not require an oxidizing agent. Hair dyeing compositions of the direct dyeing character generally comprise a blend of red, blue and yellow hair dye components. However, it is a common deficiency of such direct dye blends that the component dyes show unequal wearing properties. This deficiency may manifest itself in one or more weeks after application as the socalled off shade wearing. One aspect of this oil? shade wearing is theso-called greening effect which can be attributed to the fact that the commonly used blue 'and red dye components tend to wear off the hair at a faster rate than the common yellow components. Where the dye composition contains only yellow and red components the faster rate of wear of the red component (as compared with the commonly used yellow components) cause a yellowing of the dyed hair. 7

It appears that the blue and red dye components now employed in dyes of the character are more susceptible to wet treatment (such as shampooing, exposure to perspiration) and more sensitive to other weathering effects, including light exposure, than the yellow dyes now commonly used in these composition-s. Accordingly, the problems of off shade wearing is most serious in these situations wherein the hair is most subject to these conditions. Thus,

for example, the greening effect is most prevalent in closcropped hair (e.g. at the temples) or in short coifiures or on mens heads. Moreover, in these short hair areas, the loss of dye is more readily apparent.

It has now been found that the so-called off shade wearing effect can be eliminated by incorporating in the dye composition as the yellow component certain dye or dyes which are changed, destroyed, leached or otherwise removed from the hair at substantially the same rate as the blue and/or red components. In this fashion the loss 7 is equalized and the balance of shade during wearing is not upset.

It is accordingly an object of the present invention to provide a dye composition, which when applied to human hair, will not exhibit the so-called oflf shade wearing.

It is also an object of the present invention to provide a process for dyeing hair using the dyeing compositions described in the above object.

Other andmore detailed objects will be apparent from the following description and claims.

The class of dyes that have been found to be especially applicable to the present invention are hydroxyalkyl nitroanilines described by the formula:

NO: I

wherein R- is hydrogen, lower alkyl or hydroxyalkyl and R is hydroxyalkyl.,R and R can be the same hydroxyalkyl radical or. they may represent diiferenthydroxyalkyl radicals. In the preferred form of this invention the hydroxyalkyl radical has from 1 to 4 cabon atoms and l, 2 or 3 hydroxy groups. Moreover, the ortho and para compounds are preferred.

When R or R are hydroxyalkyl, they can be any of a variety of straight-chain or branched-chain radicals. By way of illustration, the following hydroxyalkyl radicals may be mentioned: Z-hydroxyethyl; Z-hydroxypropyl; 3- hydroxypropyl; 2,3-dihydroxypropyl; 4-hydroxybutyl; 2- methyl-l,3-dihydroxy 2 propyl; tris(hydroxymethyl) methyl.

It is surprising that dyes of this structure should have sufficient afiinity tohair to be valuable in hair coloring compositions. In general, there are few non-ionic (i.e. disperse) dyes of any shade which have afiinity to hair under the mild conditions required, i.e. at room temperature. These disperse dyes which do have aflinity generally have more complex structures, that is, they have additional functional groups (such as hydroxyl or amino) on the benzene nucleus which are available for binding to the substrate or they have multiple nuclei as in naphthoquinones, anthraquinones or azo dyes.

The hydroxyalkyl nitroaniline dyes of Formula 1 above, as the yellow component, may be used in conjunction with any of the blue, red or violet dye components conventionally used in hair dye compositions. These latter dye components are generally lower in wash fastness, and/or perspiration fastness and in general fastness to conditions of weathering and wearing than the yellow components conventionally used in hair dyes.

These dyes can be chosen from any of the various classes of dyes, the sole requirement being that they be relatively low in wet fastness when applied to hair. In general, however, the blue, red and violet dyes will be chosen from the acid or disperse (non-ionic) classes of dyes, since such dyes tend particularly to poor wet fastness on hair.

As regards structure, they may be from the nitro, naphthoquinone, anthraquinone, or azo series of dyes. As examples of acid dyes that are suitable may be mentioned the blue, red and violet acid dyes which appear among the United States Food, Drug and Cosmetics dyes, or listed,.for example, in the Colour Index, second edition, pp. 1800-1802. As examples of disperse dyes which are suitable may be mentioned naphthoquinones such as 2-hydroxy-, 5-hydroxy-, and 5,8-dihydroxy-1,4-naphthoquinone; 5-amino-8-hydroxy-1,4-naphthoquinone 1 imine (the so-called naphthazarine intermediate; derivative products of naphthazarine intermediate with alkyl and arylamines; anthaquinones such as quinzarin, chrysazin,

anthraquinone; l-hydroxy-2,4-bis (p dimethylaminoanilino anthraquinone; 1,4-diamino-2- (hydroxyethoxyethoxy) anthraquinone and the like; azo dyes such as N,N-bis- (hydroxyethyl)-4-(p-nitrophenylazo)aniline. A class of red, violet and blue dyes which is particularly preferred for the operation of this invention is the class of nitro dyes of the nitrophenylenediamine structure such as 2-nitro-p-phenylenediamine and its N-alkylated derivatives, such as those described in US. Pats. 3,088,877; 3,088,- 878; 3,168,442; 2,750,326; 2,750,327; 3,049,393; 3,117,- 911; and the like The relative amounts of hydroxyalkyl nitroaniline dye (yellow components), blue component and red component obviously will vary with the particular shade desired and the individual dyes selected. In general, however, they will be present within the following ranges:

Percent by wt. of total composition (a) Hydroxyalkyl nitroaniline 0.001 to 0.15 (b) Blue component 0.005 to 0.50 (c) Red component 0.001 to 0.20

The pH of the dye compositions of this invention can also vary widely, e.g. from about 4 to 11. In the acid range the pH of about 5 to 7 is suitable. It is preferred, however, that the compositions be in the alkaline range, and particularly at a pH of about 7.5 to 10 when dyeing human hair. Any selected water-dispersible, compatible, alkalizing agent employed can vary over a wide range depending on the dye and particular alkalizing agent employed and the desired pH. lllustratively, the alkalizing agent can vary from less than about 0.1% to about 10% by weight of the composition.

The alkalizing agent is selected so that it will not interfere (i.e. is compatible) with the dye employed, and will not precipitate the dye. When used to dye human hair on the head, the alkalizing agent must be non-toxic under the conditions of use, and not injure the scalp at its ultimate concentration in the composition to be applied. A preliminary test of some selected alkalizing agent can be made to note its compatibility with the dye or to discover possibility of toxicity or injury.

Ammonium hydroxide, because of its freedom from toxicity over a wide concentration range and its economy, is an acceptable alkalizing agent. However, there can be used in place of, or together with, ammonia any other compatible ammonia derivative as an alkalizing agent, such as an alkylamine, such as ethylamine, dipropylamine, or triethylamine, such as 1,3-diaminopropane, an alkanolamine, such as ethanolamine or diethanolamine, a polyalkylenepolyamine, such as diethylenetriamine, or a heterocyclic amine, such as morpholine.

Also, as alkalizing agent, any alkaline earth hydroxide, for example, calcium hydroxide or magnesium hydroxide, can be used up to the limit of its water solubility and at any concentration that fails to product a precipitate with any of the components of the composition. The dissolved alkaline earth hydroxides are preferred over the alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, or carbonates, such as sodium carbonate and bicarbonate. Any of these can also be used so long as their ultimate concentration in the final dyeing solution is below that which might possibly irritate the scalp.

The alkalizing component of choice, however, is a water-soluble organic amine of low volatility (B.P. higher than about 50 C.) having less than about 12 carbon atoms, such as n-propylamine, isobutylamine, 2-ethylbutylamine, diethylamine, triethylamine. Particularly suited as the alkalizing agents are the following: (A) primary aliphatic diamines, such as ethylenediamine; 1,2-diaminopropane; 1,3-diaminopropane; diethylenetriamine; triethylenetetramine; 2,2'-iminodipropylamine; 3,3-iminodipropylamine; and bis-hexamethylenetriamine; (B) alkanolamines, such as ethanolamine; isopropanolamine; di-

ethanolamine; di-isopropanolamines; triethanolamine; triisopropanolamine; N-methyldiethanolamine; di-isopropylethanolamine; dimethylisopropanolamine; 2 amino-2- methylpropane 1,3 diol; tris(hydroxymethyl)methylamine and the like, which may also have a phenyl substituent, e.g. N-(2-hydroxyethyl)aniline; N-methyl-N-(2- hydroxyethyl)aniline; N,N-bis(2 hydroxyethyl)aniline; and (C) heterocyclic amines, such as morpholine, N-methylmorpholine, N-cthylmorpholine, N-hydroxyethylmorpholine, N-phenylmorpholine, piperidine, N-hydroxyethylpiperidine, and piperazine.

The pH of the composition may be adjusted with any inorganic or organic acid or acid salt which is compatible with the composition. Illustrative of acids or acid salts there can be mentioned: sulfuric, formic, acetic, lactic, citric or tartaric acid, or ammonium sulfate, sodium dihydrogen phosphate, or potassium bisulfate.

Water-soluble surface active agents can also be employed in the dyeing compositions utilized in this invention. These can be anionic, non-ionic or cationic. Illustrative of the various types of water-soluble surface active agents there can be mentioned: higher alkylbenzenesulfonates; alkylnaphthalenesulfonates, sulfonated esters of alcohols and polybasic acids; taurates; fatty alcohol sulfates; sulfates of branched chain or secondary alcohols; alkyl dimethylbenzyl ammonium chlorides, and the like. Illustrative of specific surfactants there can be mentioned: lauryl sulfate; polyoxyethylene lauryl ester; myristyl sulfate; glyceryl monostearate; sodium salt of palmitic methyl taurine; cetyl pyridinium chloride; lauric diethanolamide; polyoxyethylene stearate; stearyl dimethyl benzyl ammonium chloride; dodccyl benzene sodium sulfonate; nonyl naphthalene sodium sulfonate; dioctyl sodium sulfosuccinate; sodium N-methyl-N-oleoyl taurate; oleic acid ester of sodium isothionate; sodium dodecyl sulfate; the sodium salt of 3,9-diethyl tridecanol-G-sulfate and the like. The quantity of water-soluble surface active agent can vary over a wide range, such as that of from about 0.01% to 20% and preferably from about 0.10% to 10% by weight of the composition.

A thickening agent can also be incorporated in the present dyeing composition. One or several of those commonly used in hair dyeing, such as sodium aliginate or gum arabic, or cellulose derivatives, such as methyl cellulose, or the sodium salt of carboxymethylcellulose, or acrylic polymers, such as polyacrylic acid sodium salt, or inorganic thickeners, such as bentonite may be used to advantage. When used, the quantity of thickening agent can vary over a Wide range, such as that of from about 0.1% to 20% and preferably from about 0.5% to 5% by weight.

The water content of the composition is ordinarily the major constituent and can also vary over a wide range dependent in large measure on the quantity of other additives. Thus, the water content can be as little as 10%, and preferably from about 70% to 99%.

The dyeing compositions of this invention are preferably aqueous compositions. The term aqueous composition is used herein in its generic sense as embracing any water-containing composition embodied in the invention. This includes true solutions of the dye in an aqueous medium, either alone or in conjunction with other materials, which are also dissolved or dispersed in the aqueous medium. The term aqueous composition also encompasses any mixture of dye with the aqueous medium either alone, or together with other ingredients. The dye may be colloidally dispersed in the medium or may merely be intimately mixed therein.

The term aqueous medium, as used herein, includes any medium which contains water. Thus, the aqueous medium may be an aqueous alkaline, aqueous neutral or aqueous acid medium. Moreover, the aqueous medium may comprise water and a solvent, e.g. ethanol. The latter may be employed as a common solvent to enhance the solution of the dye or some other organic material.

The aqueous compositions of this invention may take many forms. Thus, they may be thin or thick flowable liquids, pastes, gels, etc.

Typical dyeing compositions which are particularly suitable for dyeing human hair are set forth below:

(1) ALKALINE COMPOSITIONS Any of the dyes, surface active agents, alkalies, thickening agents, acids and combinations thereof set forth above may be used in the proportions specified in the table immediately above.

(2) ACID COMPOSITIONS The acid compositions are similar to the above alkaline compositions, except that the alkali is omitted, and the acid is added to a pH of 2.5-7, preferred 3.5-7.0. The surfactant may be anionic, cationic or non-ionic or suitable mixtures of these, and any of those mentioned above may be used. In certain cases the surfactant itself acts as a thickener.

The dyeing compositions of this invention can be prepared by the conventional methods used in this art. Thus, they can be prepared by dissolving or suspending the dye in water in the desired concentration. Water miscible organic solvents can be employed to facilitate solution of the dye; in this event, the dye can be dissolved first in the solvent and then diluted with water. The dispersion of the various ingredients can also be facilitated by heating the composition at temperatures varying from 40 C. to 110 C., either before dilution with water or afterwards.

The dyeing compositions of this invention can be applied to hair by the conventional techniques used in the art. Illustratively, when applied to living hair on the human head, the compositions can be applied to the hair with a brush, sponge, or other means of contact, such as dipping until the hair is properly saturated with the composition.

The reaction time or time of contact of the dyeing composition With the hair is not critical and can vary over a wide range used in the hair dyeing art, such as periods of about 5 minutes to about 2 hours, and preferably from about 5 minutes to about 60 minutes. The dyeing temperature can vary over wide limits as is conventional in the art. Thus, the dyeing temperature can vary from about room temperature, e.g. about 20 C.

The following examples are further illustrative of the present invention. It should be understood, however, that the invention is not limited thereto.

DYEING PROCEDURE A Dyeing hair with alkaline compositions (pH -7 or higher) A mixture was prepared using specified amounts of the following components:

Dyes Amount to be specified. Isopropanol 0.5 ml.

Alkaline agent Amount to be specified. Surface-active agent Do.

Thickening agent Do.

The dyes were first wet with isopropanol and the above listed agents were added, as well as 50 ml. water. The mixture was then heated at 60 C. with stirring until a uniform dispersion was obtained. The mixture was then further diluted with water to a volume of ml. and citric acid was added to give a final, specific pH of 7 or higher. The dyeing composition so obtained was poured on natural gray hair or bleached hair and allowed to remain in contact with the hair for 20 minutes at 30 C. Afterwards, the hair was rinsed in clear water and dried.

EXAMPLE 1 Hair was dyed according to Procedure A, using 0.050 g. N-(2-hydroxyethyl-o-nitroaniline; 0.005 g. N -(2-hydroxyethyl-2-nitro-p-phenylenediamine, 3.0 g. N-phenyldiethanolamine (as alkaline agent), 3.0 g. sodium N-coconut acid N-methyl taurate (as surfactant) and 3.0 g. hydroxyethylcellulose (as thickener), the pH being adjusted to 9.5. Both gray and bleached hair were dyed in blonde shades fast to shampooing.

When these were subjected to successive shampooings, to treatment with acid and alkaline perspiration, and to light fastness tests, the dyeings became more or less weaker, but with no significant change of hue. When the dye composition was applied to living human air (bleached) on the head and the shade worn for six weeks, with normal periodic shampooing, exposure to light and weathering, there was no essential change in the hue or tone of shade, though strength loss gradually occurred.

EXAMPLE 2 Gray hair was dyed according to Procedure A, using 0.15 g. N-(Z-hydroxyethyl)-onitroaniline; 0.35 g. N ,N ,N tris(hydroxyethyl)-2-nitro-p-phenylenediamine; 0.25 g. 2- nitro-p-phenylenediamine (red component); 3.0 diethylenetriamine (alkaline agent), 4.0 g. lauric diethanolamide (surfactant) and 3.0 g. methylcellulose (thickener), the pH being adjusted to 8.5.

The hair was dyed a uniform medium brown shade fast to rubbing. The dyeings were subjected to three successive shampooings; also to fastness tests in acid and alkaline perspiration according to the AATCC Colorfastness Perspiration Test; also to light fading in the Fadeometer. In all cases the shade losses were on tone, the final shades after the fastness tests being essentially the same in tone, though more or less weaker, than the initial shade.

The dye composition was also applied to living human hair on the head, giving again a medium brown shade, which after wear of six weeks, with concomitant normal exposure to sunlight, perspiration, periodic shampooing, and weathering, lost its color gradually but always on tone.

EXAMPLE 3 Gray and bleached hair were dyed according to Procedure A, using 0.005 g. N (2-hydroxyethyl)-o-nitroaniline, 0.075 g. N -methyl-N ,N -bis(2-hydroxyethyl)-2- nitro-p-phenylenediamine, 0.002 g. 2-nitro-p-phenylene-diamine, 4.0 g. triethanolamine (alkali), 0.75 g. sodium N- methyl-N-oleoyltaurate (surfactant) and 3.0 g. sodium carboxymethylcellulose, and adjusting the pH to 10.

The hair was dyed a silvery gray color, which showed essentially no change of hue on shampooing, or exposure to acid or alkaline perspiration, or to light. When dyed on living gray or bleached hair on the head, the dyeings maintained their initial hue, though with some strength loss, after six weeks of wearing.

EXAMPLE 4 Gray hair was dyed according to Procedure A: 0.05 N- (2-hydroxyethyl)-o-nitroaniline, 0.003 g. N -methyl-N N -bis-(Z-hydroxyethyl)-2-nitro-p phenylenediamine and 0.1 g. N -methyl-2-nitro-p-phenylenediamine were combined with 3 g. ethanolamine (alkali), 3 g. sodium N-coconut acid N-methyl taurate (surfactant) and 2 g. methylcellulose, at pH 8.5.

An auburn shade was obtained on the gray hair which maintained its hue on shampooing or exposure to perspiration or light. When applied to living gray hair on the head, the composition gave an auburn shade which maintained its hue after six weeks of wearing.

EXAMPLE Gray hair was dyed by Procedure A, using 0.015 g. N- (Z-hydroxyethyl)-p-nitroaniline, 0.27 g. N -methyl-2-nitrop-phenylenediamine, 0.35 g. N ,N ,N tris(2-hydroxyethyl) Z-nitro-p-phenylenediamine, 2.0 g. N-phenyldiethanolamine (alkali), 3.0 g. coconut diethanolamide (surfactant) and 1.0 g. co-polymer of acrylic acid and allylsucrose (thickener), the pH being set at 9.0. A medium brown shade was obtained on gray hair which held its tone through multiple shampoos, perspiration fastness tests, and exposure to light. Also on live gray hair on the head the hue was maintained through six weeks of wear.

EXAMPLE 6 Gray hair was dyed by Procedure A using 0.015 g. N,N- bis(2 hydroxyethyl)-p-nitroaniline, 0.33 g. N -methyl- N ,N bis(2-hydroxyethyl)-2-nitro-p-phenylenediamine, 0.28 g. 2 nitro-p-phenylenediamine, 2.0 g. 3,3'-iminodipropylamine (as alkaline agent), 3.0 g. mixed fatty acids diethanolamide (as surfactant), and 2.0 g. sodium alginate (as thickener), the pH being adjusted to 9.0. The hair was dyed a brown shade which held its tone through successive washings, and after exposure to perspiration and light. A dyeing with this composition of live gray hair on the head showed excellent wearing properties with essentially no change of hue after six weeks of normal wearing.

EXAMPLE 7 Gray hair was dyed by Procedure A, using 0.05 g. N,N- bis(2 hydroxyethyl)-p-nitroaniline, 0.003 g. N -methyl- N ,N -(2,3-dihydroxypropyl)-2-nitro-p-phenylenediamine, 0.1 g. N -(2-aminoethyl)-2-nitro-p-phenylenediamine, 1.5 g. ethylenediamine (alkaline agent), 0.75 g. sodium lauryl sulfate (surfactant), and 2.5 g. sodium carboxymethylcellulose, at a pH of 9.5. The hair was dyed an auburn shade which maintained its hue after shampooing or following exposure to perspiration or light. Gray hair on the head dyed with this composition held its color tone even after six weeks of wearing.

Although the invention has been described with reference to specific forms thereof, it will be understood that many changes and modifications may be made without departing from the spirit of this invention.

What is claimed is:

1. A dyeing composition comprising an aqueous vehicle having incorporated therein a tictorially effective amount of a dye blend comprising a yellow component and components selected from the group consisting of red components, blue components and a combination of red and blue components, said yellow component comprising a hydroxyalkyl nitroaniline dye of formula:

wherein R is hydrogen, lower alkyl or C to C hydroxyalkyl and R' is C to C hydroxyalkyl; said red and blue components being selected from the class consisting of acid dyes and disperse dyes of relatively low wet fastness when applied to hair.

2. The composition according to claim 1 wherein the hydroxyalkyl has from 1 to 3 hydroxy groups.

3. The composition according to claim 1 having a pH in the range of from about 5 to 11.

4. The composition according to claim 1 wherein the yellow component comprises from about 0.001% to 0.15% by weight of the total composition and said blue component comprises from about 0.005% to 0.50% by weight of the total composition.

5. The composition according to claim 4 including from 0.001% to 0.20% by weight of the total composition of a red component.

6. The composition according to claim 1 wherein said hydroxyalkyl nitroaniline is N-(Z-hydroxyethyl)-o-nitroaniline; said tinctorially effective amount is in the range of from about 0.001% to 0.1% by weight of the total composition; said blue or red components are of the class of nitrophenylenediamines; and the pH of said composition is in the range of from about 6 to 10.

7. The composition according to claim 4 including from 0.001% to 0.20% by weight of the total composition of a red component.

8. The composition according to claim 1 wherein the blend of dyes comprise a combination of N-(Z-hydroxyethyl) -o-nitroaniline and N (2-hydroxyethyl -2-nitro-pphenylenediamine.

9. The composition according to claim 1 wherein the blend of dyes comprise a combination of N-(Z-hydroxyethyl)-o-nitroaniline; N ,N ,N tris(hydroxyethyl)-2- nitro-p-phenylenediamine and 2-nitro p phenylenediamine.

10. The composition according to claim 1 wherein the blend of dyes comprise a combination of N-(Z-hydroxyethyl)-o-nitroaniline; N -methyl-N ,N -bis (2-hydroxyethyl)-2-nitro-p-phenylenediamine and 2-nitro-p-phenylenediamine.

11. The composition according to claim 1 wherein the blend of dyes comprise a combination of N-(Z-hydroxyethyl)-o-nitroaniline; N methyl-N ,N -bis-(Z-hydroxyethyl)-2-nitro-p-phenylenediamine and N -methyl-2-nitrop-phenylenediamine.

12. The composition according to claim 1 wherein the blend of dyes comprise a combination of N-(Z-hydroxyethyl)-p-nitroaniline; N methyl 2 nitro-p-phenylenediamine and N ,N ,N -tris(2-hydroxyethyl) 2 nitro-pphenylenediamine.

13. The composition according to claim 1 wherein the blend of dyes comprise a combination of N,N-bis(2-hydroxyethyl) p nitroaniline; N methyl-N ,N -bis (2- hydroxyethyl)-2-nitro p phenylenediamine and 2- nitro-p phenylenediamine.

14. The composition according to claim 1 wherein the blend of dyes comprise a combination of N,Nbis(2-hydroxyethyl)-p-nitroaniline; N methyl-N ,N -(2,3-dihydroxypropyl)-2-nitro p phenylenediamine and N -(2- nitro-p-phenylenediamine.

15. A method of dyeing hair which comprises applying to the hair a composition comprising an aqueous vehicle having incorporated therein a tinctorially effective amount of a dye blend comprising a yellow component and a component selected from the group consisting of red components, blue components and a combination of red and blue components, said yellow component comprising a hydroxyalkyl nitroaniline dye of formula:

wherein R is hydrogen, lower alkyl or C to C hydroxyalkyl and R is C; to C hydroxyalkyl; said red and blue components being selected from the class consisting of acid dyes and disperse dyes of relatively low wet fastness when applied to hair.

16. The method according to claim 15 wherein the hydroxyalkyl nitroaniline dye is N-(2-hydroxyethy1)-onitroaniline.

References Cited UNITED STATES PATENTS Eckardt 810.1 Eckardt 810.1 X Dohr et a1. 810.1

Brunner 810.1 Peters et a1. 8-101 Brunner et a1. 810.1

Boosen 810.1

ALBERT T.

10 Kaiser et a1 8-10.1

Ellis et a1 826 Rankin 8-25 X Lerch et a1. 826 Augustin et a1 8-10.1 X

MEYERS, Primary Examiner V. C. CLARKE, Assistant Examiner U.S. C1. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,733,175 Dated M y 25, 1973 Invenmfls) George Alper'in, et a1.

It is certified that errorappears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 8, lines 51-52, change "N -42nitro-pQphenylenediamine" to N -(2 aminoethy1)2-nitro-p-phenylenediamine Signed and sealed this 8th day of January 19714.;

(SEAL) Attest:

EDWARD M.FLETCHER,JR. RENE-D. TEG'I'D LEYER Attesting Officer Acting Commissionerof Patents FORM PC4050 USCOMM-DC 60376-P69 V U.$. GOVERNMENT PR|N T|NG OFFICE: [989 0"356'334, 

